The present invention relates to a .alpha.-oxy(oxo) sulfides and ethers.
There has been considerable work performed related to substances to (or in) various consumable materials including foodstuffs. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product. The following flavor and aroma notes are desirable, particularly in berry fruit flavored foodstuffs, vegetable flavored foodstuffs, spicey foodstuffs and citrus fruit flavored foodstuffs:
Aroma: Green/spicey, Sweet, Fruity, Fresh/fruity, Gooseberry, Concord grape, Grape, Almond, Nutty, Cereal-like, Lachrymatory onion-like, Oniony, Green onion-like, Leek, Broccoli-like, Grapefruit, Celery stalk-like, Floral, Rosey, Woody, Blackcurrant, Buchu leaf oil-like, Citronellal-like, Neroli-like, Burgamot-like, Violet leaves-like, Jasmin-like, Melony, Cucumber-like, Green, Vegetable, Sweet/floral. PA0 Flavor: Spicey, Sweet, Fruity, Milk caramel-like (dulce de leche-like), Gooseberry, Broccoli-like, Nutty, Cereal-like, Oniony, Grape, Concord grape, Citrusy, Grapefruit-like, Green fruit-like, Mandarin-like, Petitgrain-like, Blackcurrant, Minty, Astringent, Coriander-like, Green, Piney, Citronellal-like, Violet leaves-like, Melony, Green fruit-like, Cucumber, Green, Floral, Floral/green, Vegetable, Garlic. PA0 R.sup.2 represents hydrogen or together with R.sup.6 represents a dimethylmethylene group, or, when R.sup.6 is isopropyl, together with R.sup.5 represents a C--C bond, PA0 R.sup.3 represents hydrogen or together with R.sup.6 represents a dimethylmethylene group, PA0 R.sup.4 represents hydrogen or together with R.sup.1 represents a C--C bond, PA0 R.sup.5 represents hydrogen or, when R.sup.6 signifies isopropyl, together with R.sup.2 represents a C--C bond, PA0 R.sup.6 represents isopropyl or together with R.sup.2 or with R.sup.3 represents a dimethylmethylene group, PA0 R.sup.7 represents methyl, PA0 X represents a C--C double bond taking the place of a C--C single bond, PA0 m = 0 to 2, PA0 Y represents oxo bound to a primary or secondary C-atom and Z represents mercapto or lower alkylthio located in the .beta.-position to the carbonyl function, PA0 Aroma Green/spicey, Sweet, Fruity, Fresh/fruity, Gooseberry, Concord grape, Grape, Almond, Nutty, Cereal-like, Lachrymatory onion-like, Oniony, Green onion-like, Leek, Broccoli-like, Grapefruit, Celery stalk-like, Floral, Rosey, Woody, Blackcurrant, Buchu leaf oil-like, Citronellal-like, Neroli-like, Bergamot-like, Violet leaves-like, Jasmin-like, Melony, Cucumber-like, Green, Vegetable, Sweet/floral. PA0 Flavor: Spicey, Sweet, Fruity, Milk caramel-like (dulce de leche-like), Gooseberry, Broccoli-like, Nutty, Cereal-like, Oniony, Grape, Concord grape, Citrusy, Grapefruit-like, Green fruit-like, Mandarin-like, Petitgrain-like, Blackcurrant, Minty, Astringent, Coriander-like, Green, Piney, Citronellal-like, Violet leaves-like, Melony, Green fruit-like, Cucumber, Green, Floral, Floral/green, Vegetable, Garlic. PA0 p-Hydroxybenzyl acetone; PA0 Geraniol; PA0 Acetaldehyde; PA0 Maltol; PA0 Ethyl methyl phenyl glycidate; PA0 Benzyl acetate; PA0 Dimethyl sulfide; PA0 Vanillin; PA0 Methyl cinnamate; PA0 Ethyl pelargonate; PA0 Methyl anthranilate; PA0 Isoamyl acetate; PA0 Isobutyl acetate; PA0 Alpha ionone; PA0 Ethyl butyrate; PA0 Acetic acid; PA0 Gamma-undecalactone; PA0 Naphthyl ethyl ether; PA0 Diacetyl; PA0 Ethyl acetate; PA0 Anethole; PA0 Isoamyl butyrate; PA0 Cis-3-hexenol-1; PA0 2-Methyl-2-pentenoic acid; PA0 Elemecine (4-allyl-1,2,6-trimethoxy benzene); PA0 Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene); PA0 Natural blackcurrant juice; PA0 Buchu leaf oil; PA0 .alpha.-phellandrene; PA0 Cis-3-hexen-1-ol; PA0 Terpinenol-4; PA0 Ethyl maltol; PA0 Methyl benzoate; PA0 Benzaldehyde; PA0 Coriander oil; PA0 .alpha.-ionone; PA0 Ethyl heptanoate; PA0 Methyl anthranilate; PA0 Ethyl anthranilate; PA0 Cinnamic alcohol; PA0 Amyl valerinate; PA0 Cinnamyl propionate; PA0 Rhodinyl acetate; PA0 Methyl .beta.-hydroxy butyrate; PA0 Ethyl .beta.-hydroxy butyrate; PA0 2-phenyl-3-carboethoxyfuran; PA0 Cyclohexyl disulfide; PA0 Grapefruit oil; PA0 Nootkatone; PA0 Bergamot oil; PA0 Citral; PA0 Amyl alcohol; PA0 5-phenyl-4-pentenal; PA0 5-phenyl-2-pentenal; PA0 Allyl caproate; PA0 2-(n-pentyl) thiazole; PA0 2-(i-butyl) thiazole; PA0 2-(i-propyl) thiazole; PA0 2-(n-propyl) thiazole; PA0 2-phenyl-4-pentenal; PA0 2-phenyl-4-pentenaldimethylacetal; PA0 Methional; PA0 4-methylthiobutanal; PA0 2-ethyl-3-acetylpyrazine; PA0 Tetramethyl pyrazine; PA0 2-methyl pyrazine; PA0 trans-2-hexenal; PA0 Hydrolyzed vegetable protein; PA0 Monosodium glutamate; PA0 Dimethyl disulfide; PA0 Methyl propyl disulfide; PA0 Methyl propenyl disulfide; PA0 Methyl allyl disulfide; PA0 Allyl propyl disulfide; PA0 Propyl propenyl disulfide; PA0 Dipropyl disulfide; PA0 Diallyl disulfide; PA0 Propyl propenyl trisulfide; PA0 Thiopropanal-S-oxide; PA0 Thiobutanal-S-oxide; PA0 Thioethanal-S-oxide; PA0 Thiohexanal-S-oxide; and PA0 Propyl propene thiosulfonate.
Furthermore there is a continuing search for materials having desirable fragrance properties. Such materials are sought either to replace costly natural materials or to provide new fragrances or perfume types which have not heretofore been available. Especially desirable qualities for substances having interesting hyacinth fragrances, or narcisse fragrances, or violet fragrances, or oriental vetivert fragrances, or otto of rose fragrances are stability and persistence, particularly in a wide variety of perfumed articles (e.g., soaps, detergents and powders), perfume compositions and colognes, ease of manufacture and intensity of aroma.
Prior to this last decade it was the general opinion among those skilled in the art that compounds containing the mercapto or --SH moiety or substituted mercapto or --SR moiety (where R is an organic group such as alkyl or acetyl) were desirable for use in conjunction with foodstuff flavors only where alliaceous flavors were concerned, or where meaty flavors were concerned or where coffee-type flavors were concerned, and were not desirable for use in conjunction with other more delicate type flavors, e.g., blackcurrent, citrus and vegetable. However, within the last decade certain mercapto compounds have been ascertained to be useful, for example, in blackcurrant and buchu leaf oil-like flavors. In addition, within the last decade such compounds have been ascertained to be highly useful in perfumery also.
Thus, for example, British Pat. Nos. 1,423,914 and 1,423,915 issued on Feb. 4, 1976, teach that certain mercapto derivatives which are aliphatic or cycloaliphatic compounds having the formula: ##STR3## wherein X.sup.1 represents a hydroxyl group or an acyl-oxy group, and X.sup.2 represents a hydrogen atom; R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be the same or different and each represents a hydrogen atom or a univalent aliphatic hydrocarbyl group; or R.sup.1 and R.sup.3 or R.sup.4, together with the intervening carbon atoms, constitute a cycloaliphatic ring, are useful as perfuming agents as exemplified by adding 3-methylthio-hexanol to a perfume base composition of the "Fleuri" type wherein the 3-methylthio-hexanol is said to give rise to a green, fruity aroma reminiscent of that of rhubarb.
Furthermore, for example, Canadian Pat. No. 983,050 issued on Feb. 3, 1976, teaches that 3,7-dimethyl-octa-2,6-dienyl-mercaptan (thiogeraniol) of the formula: ##STR4## is used in making up a "synthetic buchu leaf oil" and imparts to a lavender type composition a greener and more herbal fragrance. USSR Pat. No. 345,677 teaches that para-menthane-8-thiol-3-one is useful as a synthetic black current flavoring for foodstuffs. This compound has the structure: ##STR5## German Offenlegungschrift Pat. No. 2,316,456, published on Oct. 11, 1973 discloses the use of certain thio alcohols or their corresponding esters in perfumery and in perfumed articles, such as detergents, cosmetics and waxes. Such mercapto alcohols having the generic structure: ##STR6## wherein R.sub.1 is a hydrocarbon moiety having from 1 up to 7 carbon atoms and R.sub.2 is one of hydrogen, methyl or ethyl.
U.S. Pat. Nos. 3,950,429 issued on Apr. 13, 1976, and 3,952,062 issued on Apr. 20, 1976, disclose certain alkylthiosubstituted oxo-terpenoids having 10 carbon atoms in the terpenoid skeleton as useful in perfumery and in flavors, particularly for providing vegetable notes. The generic structure of the compounds is as follows: ##STR7## wherein R.sup.1 represents hydrogen or together with R.sup.4 represents a C--C bond,
provided that when R.sup.2, R.sup.3 and R.sup.5 represent hydrogen, R.sup.6 represents isopropyl, R.sup.4 together with R.sup.1 represents a C--C bond, Y is .beta. to the carbon atom bearing the substituent R.sup.7 m=o, Z is .alpha. to the carbon atoms bearing the substituent R.sup.5 and .beta. to the carbon atom bearing the substituent R.sup.3, then Z represents alkylthio.
However, none of the disclosure of the prior art contains a teaching to the effect that compounds having the generic structure: ##STR8## wherein X is one of: Z is one of sulfur or oxygen; when R.sub.1 and R.sub.2 are taken separately, R.sub.1 is hydrogen or methyl, and R.sub.2 is methyl; and when R.sub.1 and R.sub.2 are taken together, R.sub.1 and R.sub.2 form phenyl moieties; and Y is one of C.sub.1 -C.sub.4 alkyl, C.sub.3 or C.sub.4 alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl have the ability to create the following aroma and flavor notes in foodstuffs:
Furthermore, other substituted mercaptans in the prior art which are shown to be useful in perfumery are indicated to have rhubarb-like, or berry, or other floral-type fragrances, e.g., ionone and irone derivatives having the structure: ##STR9##
Furthermore, certain .alpha.-mercaptoketones disclosed in the prior art, but only in meat flavors. Thus, U.S. Pat. No. 3,773,524 issued on Nov. 20, 1973, discloses the use of .alpha.-ketothiols of the formula: ##STR10## wherein R.sub.1 is methyl or ethyl; and R.sub.2 and R.sub.3 are hydrogen, methy or ethyl to alter the meat flavor and aroma of foodstuffs. U.S. Pat. No. 3,892,878, issued on July 1, 1975, discloses the use of certain hydroxy-mercaptoalkanes to alter the flavor of foodstuffs, for example, 2-mercapto-3-butanol used in meat flavors. The genus disclosed by U.S. Pat. No. 3,892,878 is as follows: ##STR11## wherein X is oxygen or sulfur, n is 0 or 1, R.sub.1 -R.sub.7 are the same or different and each is hydrogen or lower alkyl of 1-4 carbon atoms, a and b are the same or different and each represents an integer of from 0 to 10 when n is 0 and when n is 1, a and b are the same or different and each represents an integer of from 1 to 10. 3-mercaptoheptanon-4 is disclosed per se in U.S. Pat. No. 2,888,487, issued on May 26, 1959. 3-mercapto-2,6-dimethyl-heptan-4-one is disclosed in Chem. Abstracts 6478 (d) Vol. 62, 1965 (abstract of Asinger, Diem and Schaefer, Monatsh. Chem. 95 (4-5), 1335-54 (1964). Beilstein E-IV-1 discloses 2-mercapto-2,4-dimethyl-pentan-3-on page 4039, 1-mercapto-octan-2-on at page 4040; and 1-mercapto-nonan-2-on at 4052 and 1-mercapto-undecan-2-on at page 4060.
U.S. Pat. No. 3,922,366 issued on Nov. 25, 1975, discloses the enhancement of foodstuffs by addition of a small but effective flavor modifying amount of a compound of the general formula: ##STR12## wherein R.sub.1 is hydrogen or alkyl and R.sub.2 is alkyl or furfuryl. The flavor nuances which are enhanced or altered are those which are found in coffee flavors and aromas.
Furthermore, none of the disclosure of the prior art contains a teaching to the effect that compounds having the generic structure: ##STR13## wherein R is one of methyl or hydrogen; X is one of ##STR14## and Y is one of methyl, methally having the structure: ##STR15## n-propyl, 2-methyl-1-propyl or acetyl, has the ability to create an intense sweet and/or green and/or floral and/or herbal and/or vegetative and/or basil-like and/or minty and/or melony and/or grapefruit and/or fruity and/or alliaceous aroma with yara and/or neroli and/or verdima nuances as is carried out using the instant invention. Furthermore, other substituted mercaptans in the prior art which are shown to be useful in perfumery and other mecaptans in the prior art which are shown to be useful in perfumery are indicated to have rhubarb-like or berry or other type floral fragrances, e.g., ionone and irone derivatives having the structure: ##STR16## as disclosed in British Pat. No. 1,327,320, published on August 22, 1973, wherein one of the dashed lines represents a double bond, and where R is hydrogen or alkyl.